Nature Chemistry Contents March 2015 Volume 7 Number 3 pp181-264

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TABLE OF CONTENTS March 2015 Volume 7, Issue 3 Editorial Books and Arts Research Highlights Blogroll News and Views Articles In Your Element Subscribe   Facebook   RSS   Recommend to library   Twitter   Advertisement NPG Asia Materials is proud to present a web focus on materials for advanced energy conversion and storage. This web focus features a selection of articles that are related to the processes of converting and storing energy, including concepts of novel fuel cells, processing and materials for solar cells, as well as high-performance electrodes for supercapacitors and ion batteries.  Access the Web Focus today!    Editorial Top Molecular electronics under the microscope   p181 doi:10.1038/nchem.2200 The field of molecular electronics has developed significantly as experimental techniques to study charge transport through single molecules have become more reliable. Three Articles in this issue highlight how chemists can now better understand and control electronic properties at the molecular level. See also: Article by Dell et al. | Article by Su et al. | Article by Xiang et al. Books and Arts Top The inside track   p183 Tom Branson reviews Navigating the Path to Industry: A Hiring Manager's Advice for Academics Looking for a Job in Industry by M. R. Nelson doi:10.1038/nchem.2190 Research Highlights Top Polymer synthesis: Photoredox ROMP | Stimuli-responsive materials: Bursting bubbles | Asymmetric epoxidations: Challenging substrates | Subporphyrins: Hydride enters the ring Blogroll Top Blogroll: Coding chemistry   p185 See Arr Oh doi:10.1038/nchem.2187 News and Views Top Supramolecular catalysis: Terpenes in tight spaces   pp187 - 189 Jeremy J. Roach and Ryan A. Shenvi doi:10.1038/nchem.2191 The ability of enzymes to direct the synthesis of complex natural products from simple starting materials is epitomized by terpene biosynthesis. Now, a supramolecular catalyst has been shown to mimic some of the reactivity of this process. See also: Article by Zhang & Tiefenbacher Mass spectrometry: Bound in flight   pp189 - 190 Sophie R. Harvey and Vicki H. Wysocki doi:10.1038/nchem.2192 In their natural environment, membrane proteins are surrounded by lipids, but the effect that the lipids have on the proteins is not easy to assess. Now, controlling the extent of delipidation has enabled the study of these interactions. See also: Article by Bechara et al. Prebiotic chemistry: Replicating towards complexity   pp191 - 192 Irene A. Chen doi:10.1038/nchem.2188 Replication of long nucleic acid sequences was required for the evolution of biological complexity during the origin of life; however, short sequences are normally better replicators than long ones. A common physical environment now provides a simple mechanism to reverse this trend and enables long sequences to flourish. See also: Article by Kreysing et al. Interfaces: Scientists strike wet gold   pp192 - 194 Bernd Winter doi:10.1038/nchem.2189 The structure of liquid water is intensely studied, but it is not clear what happens to it when a surface is introduced. Now with the aid of X-ray spectroscopy it has been found that water molecules at the interface with a gold electrode have a different structure than in the bulk. Graphitic nanopores: Water capture in carbon cuboids   pp194 - 196 Kastumi Kaneko doi:10.1038/nchem.2193 Nanoporous carbon is attractive for separation purposes, but its use for low-pressure water capture has remained a challenge. Carbon cuboids have now been prepared that combine high hydrophilicity with a microporous architecture suitable for efficient trapping of atmospheric water vapour. Chemistry JOBS of the week Professor and Head, Department of Medicinal Chemistry and Molecular Pharmacology Purdue University PhD Postions in Organic Chemistry Friedrich Schiller University Jena Postdoctoral Fellow / Research Scientist (Green Chemistry) Institute of Bioengineering and Nanotechnology (IBN) Postdoctoral Fellow – Chemistry (#78234) California Institute for Biomedical Research Tenure-track assistant Professor of Materials Chemistry University of Copenhagen More Science jobs from Chemistry EVENT Biological and Climatic Impacts of Ocean Trace Element Chemistry 07.12.15 London, UK More science events from Articles Top Terpene cyclization catalysed inside a self-assembled cavity   pp197 - 202 Q. Zhang and K. Tiefenbacher doi:10.1038/nchem.2181 A tail-to-head terpene cyclization, which is hard to control in solution, has now been catalysed inside a supramolecular structure. Evidence indicates that a direct isomerization of a geranyl cation to the cisoid-isomer, which so far was considered unlikely in the biosynthesis, is feasible in this system. Chemical compounds See also: News and Views by Roach & Shenvi Heat flux across an open pore enables the continuous replication and selection of oligonucleotides towards increasing length   pp203 - 208 Moritz Kreysing, Lorenz Keil, Simon Lanzmich and Dieter Braun doi:10.1038/nchem.2155 How complex nucleic acids originally formed, despite dilution and degradation reactions, is not clear. Thermal gradients in rock pores have now been shown to be capable of trapping and thermo-cycling genetic polymers during replication. In this system long oligonucleotide strands are seen to outcompete short strands — a prerequisite for the evolution of replicating systems towards increasing complexity. See also: News and Views by Chen Molecular length dictates the nature of charge carriers in single-molecule junctions of oxidized oligothiophenes   pp209 - 214 Emma J. Dell, Brian Capozzi, Jianlong Xia, Latha Venkataraman and Luis M. Campos doi:10.1038/nchem.2160 Understanding the intrinsic electronic properties of building blocks in conjugated materials can provide powerful design guidelines to control charge transport, such as tuning the nature of the charge carriers. Now, single-molecule transport studies of a family of oxidized oligothiophenes have shown that their molecular length determines the dominant carrier type. Chemical compounds See also: Editorial | Article by Su et al. | Article by Xiang et al. Stereoelectronic switching in single-molecule junctions   pp215 - 220 Timothy A. Su, Haixing Li, Michael L. Steigerwald, Latha Venkataraman and Colin Nuckolls doi:10.1038/nchem.2180 Creating molecular components with controllable electronic properties is crucial to the realization of nanoscale devices. Now, a single-molecule conductance switch that operates through a stereoelectronic effect has been developed. The sub-ångström control of a scanning tunnelling microscope is used to switch reversibly between two distinct sets of rotational isomers, which differ greatly in their electronic character. Chemical compounds See also: Editorial | Article by Dell et al. | Article by Xiang et al. Intermediate tunnelling–hopping regime in DNA charge transport   pp221 - 226 Limin Xiang, Julio L. Palma, Christopher Bruot, Vladimiro Mujica, Mark A. Ratner et al. doi:10.1038/nchem.2183 Charge transport in molecular systems is typically through coherent tunnelling over a short distance or incoherent hopping over a long distance. An intermediate regime between those two transport mechanisms has now been found for DNA systems with stacked guanine–cytosine sequences. See also: Editorial | Article by Dell et al. | Article by Su et al. Synthesis and characterization of hexaarylbenzenes with five or six different substituents enabled by programmed synthesis   pp227 - 233 Shin Suzuki, Yasutomo Segawa, Kenichiro Itami and Junichiro Yamaguchi doi:10.1038/nchem.2174 A lack of general methods for making multisubstituted benzene derivatives means that only a small fraction of the huge number of possible structures based on this ubiquitous building block have been explored. Now, a programmed synthesis of hexaarylbenzenes using C–H activation, cross-coupling and [4 + 2] cycloaddition reactions has been developed that can also be applied to tetraarylnaphthalenes and pentaarylpyridines. Chemical compounds Atropselective syntheses of (−) and (+) rugulotrosin A utilizing point-to-axial chirality transfer   pp234 - 240 Tian Qin, Sarah L. Skraba-Joiner, Zeinab G. Khalil, Richard P. Johnson, Robert J. Capon et al. doi:10.1038/nchem.2173 A seven-step total synthesis of the axially chiral, dimeric tetrahydroxanthone natural product rugulotrosin A is described. The synthesis employs a one-pot Suzuki coupling/dimerization to generate the 2,2′-biaryl linkage using point-to-axial chirality transfer. Computational studies are described that rationalize the observed atropselectivity. Chemical compounds Dual-display of small molecules enables the discovery of ligand pairs and facilitates affinity maturation   pp241 - 249 Moreno Wichert, Nikolaus Krall, Willy Decurtins, Raphael M. Franzini, Francesca Pretto et al. doi:10.1038/nchem.2158 A method to identify pairs of ligands that simultaneously bind to a target protein has been developed. The method uses two DNA-encoded chemical sub-libraries that self-assemble to form stable dual-display structures, and an encoding system that can be decoded by DNA sequencing and enables both ligands to be identified. Coulomb explosion during the early stages of the reaction of alkali metals with water   pp250 - 254 Philip E. Mason, Frank Uhlig, Václav Vanek, Tillmann Buttersack, Sigurd Bauerecker et al. doi:10.1038/nchem.2161 The explosion of alkali metals in water is a typical high-school chemistry experiment, but its mechanism is not fully understood. Using high-speed cameras and molecular simulations it is now shown that a key early step in this reaction is the migration of electrons from the alkali metal into water, leading to a charging of the metal's surface and subsequent Coulomb explosion. A subset of annular lipids is linked to the flippase activity of an ABC transporter   pp255 - 262 Chérine Bechara, Anne Nöll, Nina Morgner, Matteo T. Degiacomi, Robert Tampé et al. doi:10.1038/nchem.2172 Defining the lipid composition that exists around a membrane protein complex in natural bilayers is a challenging task. Now, key lipids that are important for the structure and function of an ABC transporter have been revealed by systematically removing layers of lipids, and using mass spectrometry to monitor those that remained closely associated with the membrane protein. See also: News and Views by Harvey & Wysocki In Your Element Top First there was hydrogen   p264 Wojciech Grochala doi:10.1038/nchem.2186 Wojciech Grochala describes how the oldest, lightest and most abundant element in the universe continues to play an essential role on today's Earth. Top   Natureevents is a fully searchable, multi-disciplinary database designed to maximise exposure for events organisers. The contents of the Natureevents Directory are now live. The digital version is available here. Find the latest scientific conferences, courses, meetings and symposia on natureevents.com. For event advertising opportunities across the Nature Publishing Group portfolio please contact natureevents@nature.com More Nature Events

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